CN108295854A - A kind of multi-stage porous nano porous copper load nano cuprous oxide wire composite material and preparation method - Google Patents
A kind of multi-stage porous nano porous copper load nano cuprous oxide wire composite material and preparation method Download PDFInfo
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- CN108295854A CN108295854A CN201810088915.0A CN201810088915A CN108295854A CN 108295854 A CN108295854 A CN 108295854A CN 201810088915 A CN201810088915 A CN 201810088915A CN 108295854 A CN108295854 A CN 108295854A
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- cuprous oxide
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- 239000010949 copper Substances 0.000 title claims abstract description 97
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 77
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 77
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 title claims abstract description 59
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 229940112669 cuprous oxide Drugs 0.000 title claims abstract description 59
- 239000002131 composite material Substances 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000002070 nanowire Substances 0.000 claims abstract description 43
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 24
- 230000003647 oxidation Effects 0.000 claims abstract description 22
- 239000000758 substrate Substances 0.000 claims abstract description 13
- 239000012792 core layer Substances 0.000 claims abstract description 6
- 239000010410 layer Substances 0.000 claims abstract description 4
- 239000000975 dye Substances 0.000 claims description 34
- 229910045601 alloy Inorganic materials 0.000 claims description 33
- 239000000956 alloy Substances 0.000 claims description 33
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 26
- 229910000808 amorphous metal alloy Inorganic materials 0.000 claims description 26
- 239000000243 solution Substances 0.000 claims description 25
- 238000002844 melting Methods 0.000 claims description 16
- 230000008018 melting Effects 0.000 claims description 16
- 229910052786 argon Inorganic materials 0.000 claims description 13
- 238000005266 casting Methods 0.000 claims description 13
- 239000007789 gas Substances 0.000 claims description 13
- 238000012360 testing method Methods 0.000 claims description 13
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 11
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 10
- 239000010453 quartz Substances 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 claims description 8
- 229940043267 rhodamine b Drugs 0.000 claims description 8
- 238000005275 alloying Methods 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 7
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 7
- 239000003792 electrolyte Substances 0.000 claims description 6
- 230000006698 induction Effects 0.000 claims description 6
- 239000007832 Na2SO4 Substances 0.000 claims description 5
- 229910052697 platinum Inorganic materials 0.000 claims description 5
- 238000005498 polishing Methods 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- 238000010792 warming Methods 0.000 claims description 5
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 4
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 claims description 3
- 239000005300 metallic glass Substances 0.000 claims description 3
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 claims description 3
- 229940012189 methyl orange Drugs 0.000 claims description 3
- 229960000907 methylthioninium chloride Drugs 0.000 claims description 3
- 241000282887 Suidae Species 0.000 claims description 2
- 229910004349 Ti-Al Inorganic materials 0.000 claims description 2
- 229910004692 Ti—Al Inorganic materials 0.000 claims description 2
- 230000007797 corrosion Effects 0.000 claims description 2
- 238000005260 corrosion Methods 0.000 claims description 2
- 238000007654 immersion Methods 0.000 claims description 2
- 239000004615 ingredient Substances 0.000 claims description 2
- 235000011152 sodium sulphate Nutrition 0.000 claims description 2
- 229910013868 M2SO4 Inorganic materials 0.000 claims 1
- 239000011159 matrix material Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 12
- 230000008901 benefit Effects 0.000 abstract description 5
- 238000004064 recycling Methods 0.000 abstract description 5
- 239000000463 material Substances 0.000 description 20
- 230000015556 catabolic process Effects 0.000 description 18
- 238000006731 degradation reaction Methods 0.000 description 18
- 239000010936 titanium Substances 0.000 description 18
- 238000002474 experimental method Methods 0.000 description 13
- 238000005516 engineering process Methods 0.000 description 10
- 235000013339 cereals Nutrition 0.000 description 9
- 210000003041 ligament Anatomy 0.000 description 9
- 229910052719 titanium Inorganic materials 0.000 description 9
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 7
- 239000011148 porous material Substances 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 6
- 229910052724 xenon Inorganic materials 0.000 description 6
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 6
- 229910052726 zirconium Inorganic materials 0.000 description 6
- 230000001699 photocatalysis Effects 0.000 description 5
- 238000007146 photocatalysis Methods 0.000 description 5
- 241000209094 Oryza Species 0.000 description 4
- 235000007164 Oryza sativa Nutrition 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000005286 illumination Methods 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 235000009566 rice Nutrition 0.000 description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000006056 electrooxidation reaction Methods 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 230000002000 scavenging effect Effects 0.000 description 3
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- -1 Methylene Chemical group 0.000 description 2
- 239000011157 advanced composite material Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 235000012149 noodles Nutrition 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 208000037656 Respiratory Sounds Diseases 0.000 description 1
- 238000007743 anodising Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000006701 autoxidation reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000011858 nanopowder Substances 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000009738 saturating Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- STZCRXQWRGQSJD-UHFFFAOYSA-M sodium;4-[[4-(dimethylamino)phenyl]diazenyl]benzenesulfonate Chemical compound [Na+].C1=CC(N(C)C)=CC=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-UHFFFAOYSA-M 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/348—Electrochemical processes, e.g. electrochemical deposition or anodisation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
-
- B01J35/39—
-
- B01J35/58—
-
- B01J35/60—
-
- B01J35/643—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0081—Preparation by melting
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
Abstract
A kind of multi-stage porous nano porous copper loads nano cuprous oxide wire composite material, which is strip, including noncrystal substrate, the nano porous copper that is covered on noncrystal substrate and the cuprous nano wire of porous oxidation for being supported on nano porous copper surface.Wherein, which is 5 layers, and intermediate core layer is noncrystal substrate, and intermediate core layer both side surface is covered with nano porous copper, and the cuprous nano wire of porous oxidation in both sides nano porous copper area load.Wherein unilateral 6~12 μm, tough 20~40nm of bandwidth, 15~30nm of aperture size of nano porous copper thickness, 3~12 μm of unilateral nano wire thickness, 5~10 μm of nanometer line length, wide 5~10nm；The nano aperture that size is 0.5~2nm is dispersed on nano wire.Present invention process is simple, short preparation period；Prepared composite material possesses good mechanical integrity, is recycled recycling, and economic benefit is improved.
Description
Technical field：
The present invention relates to cuprous oxide field of material technology, specifically a kind of multi-stage porous nano porous copper load oxidation
Cuprous nanowire composite and preparation method thereof.
Background technology：
Cuprous oxide is a kind of p-type narrow band gap (2.17eV) semi-conducting material, active electron-hole pair system, because
This shows good catalytic activity, shows prodigious application potential in photocatalytically degradating organic dye etc..Many institutes
Known, the degradation property of catalyst is often depending on its effective surface area and porosity.Therefore nanosizing and porous, are to carry
The effective ways of high cuprous Photocatalytic Degradation Property.
First technology, publication number CN104556198A " a kind of continuous production method of ultrafine cuprous oxide and its are answered
With ", in the patent, the product of preparation is cuprous nano powder, and preparation process needs carry out in pressure-resistant tubular reactor,
Reaction pressure is up to 20MPa, increases manufacturing cost.Before carrying out catalytic degradation organic dyestuff with the powder sample, urged containing this
The methyl orange solution of change material need to stir 1 hour under dark surrounds could carry out illumination, and Material handling processes is made to become more
It is complicated.Powder sample is easy mutually to block and accumulate, and reduces catalytic efficiency.And it is not easy to recycle after application, increases and cause
The possibility of secondary pollution.
First technology, publication number CN106629812A " a kind of preparation method of nano cuprous oxide wire material ", the patent
In, it needs to impregnate nano porous copper obtained 1~4 day in absolute ethyl alcohol, nano cuprous oxide wire could be generated.The material
Long preparation period, and nano cuprous oxide wire is thicker, diameter about 20nm, toughness is poor, is easily broken off, and affects the material conduct
The performance and efficiency of photocatalytic degradation agent.
Invention content：
The purpose of the present invention is easily to be accumulated for powder visible light catalytic material in current techniques, is not easily recycled, is easy to draw
Send out secondary pollution；The deficiencies of nano cuprous oxide wire material preparation period is long, size is relatively thick, easy fracture, provides a kind of multi-stage porous
Nano porous copper loads nano cuprous oxide wire composite material and preparation method.The material includes noncrystal substrate nano porous copper
Composite strip and the cuprous superfine nanowire of the porous oxidation for being supported on its surface, i.e., with multi-stage porous, (nano porous copper is received
The nano-pore on micron openings-nano wire between metre hole-nano wire) structure composite material.Preparation method is will to be first made
Amorphous alloy ribbon be heat-treated, remove the residual stress inside amorphous alloy ribbon, then used in de- alloying technology
H2SO4It impregnates, nano porous copper autoxidation is allowed to form cuprous oxide site, cuprous oxide is formed will pass through anode oxidation process
Nano wire.A kind of multi-stage porous nano porous copper load nano cuprous oxide wire composite material is finally made.Prepared by the present invention
Composite material has the specific surface area of bigger and more active sites compared to what is reported at present.And it is finer and closely woven, flexible
Nano wire so that it is occupied unique structure and performance advantage in photocatalytically degradating organic dye field.
The technical scheme is that：
A kind of multi-stage porous nano porous copper load nano cuprous oxide wire composite material, the composite material are strip, including
Noncrystal substrate, the nano porous copper being covered on noncrystal substrate and the porous oxidation for being supported on nano porous copper surface is cuprous receives
Rice noodles.Wherein, which is 5 layers, and intermediate core layer is noncrystal substrate, and intermediate core layer both side surface is covered with nanometer
Porous Cu, and the cuprous nano wire of porous oxidation in both sides nano porous copper area load.The noncrystal substrate is
CuxZryTizAlwAlloying component, wherein x, y, z, w are atomic percent, 45≤x≤50,20≤y≤25,25≤z≤30,5≤
W≤10 and x+y+z+w=100；Wherein unilateral 6~12 μm, tough 20~40nm of bandwidth of nano porous copper thickness, aperture size 15~
30nm, 3~12 μm of unilateral nano wire thickness, 5~10 μm, wide 5~10nm of nanometer line length, every 20~30 nano wire clusters are at one
Beam；The nano aperture that size is 0.5~2nm is dispersed on nano wire.
The preparation method of the multi-stage porous nano porous copper load nano cuprous oxide wire composite material, including walk as follows
Suddenly：
The first step prepares amorphous alloy ribbon
According to target the proportioning of ingredient weighs pure Cu, pure Zr, pure Ti and pure Al；It is put into vacuum arc melting furnace and melts after cleaning
Cu-Zr-Ti-Al alloy pigs are refined to obtain, are placed in quartz test tube through polishing, cleaning, quartz test tube, which is put into vacuum, gets rid of band machine
It is fixed in middle induction coil, induction melting is carried out under high-purity argon gas protection, molten metal liquid is blown into cast into non-crystaline amorphous metal
Band；Wherein：Melting and get rid of band vacuum degree be 9 × 10-4Pa；It is 0.5~2.0MPa to blow casting pressure；Blow casting non-crystaline amorphous metal obtained
Bandwidth is 1.5~2mm, and thickness is 20~40 μm；
Amorphous alloy ribbon is heat-treated by second step
Amorphous alloy ribbon obtained in the previous step is placed in tube furnace, in the case of logical argon gas, with 5~10 DEG C of min-1
Speed from 25 DEG C of temperature programmings to 150 DEG C, after constant temperature keeps 1~3h, then with 5~10 DEG C of min-1Speed program be warming up to
250 DEG C, constant temperature takes out after keeping 1~3h；
Third walks, and de- alloy treatment prepares nanoporous copper metal
Amorphous alloy strips obtained in the previous step are placed in 4~8h of immersion in HF corrosive liquids, obtain nanoporous copper metal；
Corrosion temperature is 298K constant temperature, a concentration of 0.01~0.05M of HF corrosive liquids；Then in the H of 0.1~0.25M2SO4It is impregnated in solution
60~90 seconds；
4th step, anodic oxidation prepare multi-stage porous nano porous copper load nano cuprous oxide wire composite material
Using platinum electrode as cathode, previous step passes through H2SO4The nanoporous copper metal that solution impregnates is as DC power supply sun
Pole carries out anodic oxidation；Composite material obtained is placed in drying box in 50~150 DEG C of dry 1~2h, multi-stage porous is obtained and receives
Rice Porous Cu loads ultrafine cuprous oxide nanowire composite；
Wherein, in anodic oxidation reactions, the mixed solution of electrolyte sodium hydroxide and sodium sulphate, in mixed solution, NaOH
A concentration of 0.5~1M, NaOH and Na2SO4Molar ratio be 2:1；0.5~20mA of current density cm-2, the reaction time 5~
60min, 20~30 DEG C of reaction temperature.
The pure Cu, pure Zr, pure Ti and pure Al purity be mass fraction be 99.99%.
The application of the multi-stage porous nano porous copper load nano cuprous oxide wire composite material, is used for photocatalytic degradation
Organic dyestuff.
The organic dyestuff is preferably rhodamine B, one or more in methyl orange and methylene blue.
A kind of above-mentioned multi-stage porous nano porous copper loads nano cuprous oxide wire composite material and preparation method, used
Raw material and equipment obtained by well known approach, operating procedure used, which is those skilled in the art, to be slapped
It holds.
The present invention substantive distinguishing features be：
The present invention has unique difference from the design feature and preparation method of cuprous oxide composite material：
(1) nano cuprous oxide wire obtained in current techniques, surface do not have pore space structure, and produced by the present invention receive
Nanowire surface is dispersed with the hole of a large amount of nanoscales, forms a kind of multi-stage porous nano porous copper load cuprous oxide superfine nano
Line composite material has the multi-stage porous (nanometer on micron openings-nano wire between nano-pore-nano wire of nano porous copper
Hole) structure composite material.Therefore the specific surface area for improving material, provides more reactivity sites.And it is ultra-fine
Cuprous oxide have certain flexibility and integrality.High-specific surface area, ultrafine cuprous oxide nano wire make it be dropped in photocatalysis
Unique structure and performance advantage are occupied in solution organic dyestuff field.
(2) in current techniques, de- alloy is often carried out with alloy thin band, since there are residual stress for alloy thin band, is made
Nano porous copper it is easily cracked and broken, and then prepared cuprous oxide composite material is made to lose mechanical integrity.
Heat treatment process, de- alloying technology and anode oxidation process are combined to explore a whole set of and prepare by this patent has machinery complete
The novel preparation process of the cuprous oxide composite material of property.
Compared with existing technology, beneficial effects of the present invention are as follows：
(1) present invention prepares one kind and having both the multi-stage porous (micron between nano-pore-nano wire of nano porous copper for the first time
Nano-pore on hole-nano wire) structure advanced composite material (ACM), including noncrystal substrate nanoporous copper composite strip and load
The cuprous superfine nanowire of porous oxidation on its surface.Wherein de- alloy can prepare tough 20~40nm of bandwidth, aperture size 15
The nanoporous copper metal of~30nm.5~10 μm of length is prepared on its surface followed by anodizing technology, wide 5~10nm's
The cuprous nano wire of porous oxidation.Nanoporous size on nano wire is 0.5~2nm.The composite material can efficiently drop in photocatalysis
Solve organic dyestuff.
(2) heat treatment process, de- alloy technology and anode oxidation process are dexterously combined together preparation one by the present invention
Kind of multi-stage porous nano porous copper loads ultrafine cuprous oxide nanowire composite, and the preparation process is simple, short preparation period；Institute
The composite material of preparation possesses good mechanical integrity, is recycled recycling, and economic benefit is improved.
(3) compared with publication number CN106629812A nano cuprous oxide wires diameter about 20nm, the oxygen prepared by the present invention
Change that cuprous nanowire diameter is thinner, and is dispersed with the nano aperture that a large amount of size is 0.5~2nm on nano wire.Therefore possess
More abundant porosity and more reactivity sites.Be conducive to the infiltration of solution and the transmission diffusion of ion, increase saturating
Light rate and light absorption quickly and efficiently carry out to be conducive to photocatalytic degradation.The structure is used as photocatalytically degradating organic dye
Degradation efficiency can be improved 20 times or more.
Description of the drawings：
Fig. 1：The XRD spectrum of the nano cuprous oxide wire prepared in embodiment 1.
Fig. 2：The stereoscan photograph of the nano cuprous oxide wire prepared in embodiment 1.
Fig. 3：Stereoscan photograph under the nano cuprous oxide wire high power prepared in embodiment 1.
Fig. 4：The transmission electron microscope photo of the nano cuprous oxide wire prepared in embodiment 1.
Specific implementation mode
Embodiment 1
Select alloying component Cu50Zr20Ti25Al5, the atomic percent according to each element in subject alloy：Cu is
50at.%, Zr 20at.%, Ti 25at.%, Al 5at.% weigh the high-purity copper sheet that mass fraction is 99.99%
(7.525g), zirconium grain (4.321g), titanium grain (2.835g) and aluminium flake (0.32g) obtain master alloy raw material 15g；By master alloy raw material
It is placed in vacuum arc melting furnace and (is put into the pure titanium grain of 99.9wt% before melting as oxygen scavenging material), under high-purity argon gas protection
Melt back 4 times (ensure the uniformity of alloy), each 40s or so.Cool to the furnace room temperature to get to
Cu50Zr20Ti25Al5Alloy pig.
3~4g of alloy pig after taking polishing to clean is placed in quartz test tube, and quartz test tube is put into vacuum and is got rid of in band machine and is felt
It answers in coil and fixes, carry out induction melting under high-purity argon gas protection, and molten metal liquid is blown into casting under certain pressure difference
Form amorphous alloy ribbon；It is 1.0MPa to blow pressure needed for casting, and vacuum degree is 9.0 × 10-4Pa blows casting amorphous alloy thin obtained
Bandwidth is 2mm, and thickness is 25 μm；
The sample that several 30mm long are intercepted on the amorphous alloy thin band of acquisition is placed in tube furnace, in the feelings of logical argon gas
Under condition, with 5 DEG C of min-1Speed from 25 DEG C of temperature programmings to 150 DEG C, after constant temperature keeps 2h, then with 5min-1Speed program liter
To 250 DEG C, constant temperature takes out temperature after keeping 2h.
Amorphous alloy ribbon obtained in the previous step is placed in 0.05M HF solution and takes off alloy treatment 4h, ligament and hole is made
The uniform nano porous copper of diameter.There is nano porous copper obtained uniform, co-continuous ligament/pore space structure three-dimensional (3D) to receive
Meter Duo Kong patterns.Unilateral nanoporous copper thickness is 7 μm, ligament width 20nm, aperture size 15nm.Then in 0.1M
H2SO4It is impregnated 90 seconds in solution.
Using platinum electrode as cathode, the nano porous copper prepared cleans, is used as anode to carry out electrochemical oxidation after drying,
Experiment condition is that will contain 0.5M NaOH and 0.25M Na2SO4Mixed solution as electrolyte, current density 10mA cm-2,
Reaction time 10min, 20 DEG C of reaction temperature；It is cleaned with deionized water after taking-up, is placed in drying box in 50 DEG C of dry 2h, obtains
Nano cuprous oxide wire composite material is loaded to multi-stage porous nano porous copper；Fig. 1 is that the cuprous oxide prepared in the present embodiment is received
The XRD spectrum of rice noodles.It can prove that nano cuprous oxide wire is successfully made in the present embodiment.Fig. 2 is prepared in the present embodiment
Nano cuprous oxide wire stereoscan photograph, Fig. 3 is sweeping under the nano cuprous oxide wire high power prepared in the present embodiment
Retouch electromicroscopic photograph.It is observed that nano cuprous oxide wire is closely supported on nanoporous copper metallic face, unilateral nano wire layer
5 μm thick, 5 μm, wide 10nm of nanometer line length, every 20~30 nano wire clusters are at a branch of.Fig. 4 is the oxidation prepared in the present embodiment
The transmission electron microscope photo of cuprous nano wire.It can be seen that having sizes of about the porous of 1nm on nano cuprous oxide wire.
The multi-stage porous nano porous copper load nano cuprous oxide wire composite material made from the present embodiment carries out photocatalysis
The experimentation of degradating organic dye is as follows：
Organic dyestuff rhodamine B is selected to carry out photocatalytic degradation experiment, solution is by 7ml 15mg L-1Rhodamine B and
3ml20wt.%H2O2Oxidant form, using the xenon lamp of 500W as light source, xenon lamp between the solution that is degraded at a distance from be
10cm, intensity of illumination are 100mW cm-2.When experiment, multi-stage porous nano porous copper obtained load nano cuprous oxide wire is answered
Condensation material immerses in solution, investigates the test case of solution after dyestuff degradation different time, and the wherein relative absorbency of dyestuff is logical
Ultraviolet-visible spectrophotometer (Lambda-750PerkinElmer) is crossed to be tested.Using obtained compound in the present embodiment
Material respectively to organic dyestuff rhodamine B degradation 0,1,2,3, after five minutes, by solution relative absorbency compare it is found that at any time
Between extend to 5 minutes, dyestuff is degradable.The material carries out cycle degradation experiment, finds to congruent, different batches dyestuffs
The degradation rate for (each recycling 5min) after 5 cycles of degradation is still more than 98.6%.Illustrate that the made multi-stage porous of the present embodiment is compound
There is material the performance of good photocatalytically degradating organic dye, the performance to have benefited from the multi-stage porous (nanometer of composite material itself
The nano-pore on micron openings-nano wire between nano-pore-nano wire of Porous Cu) structure advantage, while also having benefited from material
Good flexibility and mechanical integrity so that the cuprous nano wire of porous oxidation connects with nanoporous Copper substrate during the reaction
It connects good.
Embodiment 2
Select alloying component Cu50Zr20Ti25Al5, the atomic percent according to each element in subject alloy：Cu is
50at.%, Zr 20at.%, Ti 25at.%, Al 5at.% weigh the high-purity copper sheet that mass fraction is 99.99%
(7.525g), zirconium grain (4.321g), titanium grain (2.835g) and aluminium flake (0.32g) obtain master alloy raw material 15g；By master alloy raw material
It is placed in vacuum arc melting furnace and (is put into the pure titanium grain of 99.9wt% before melting as oxygen scavenging material), under high-purity argon gas protection
Melt back 4 times (ensure the uniformity of alloy), each 40s or so.Cool to the furnace room temperature to get to
Cu50Zr20Ti25Al5Alloy pig.
3~4g of alloy pig after taking polishing to clean is placed in quartz test tube, and quartz test tube is put into vacuum and is got rid of in band machine and is felt
It answers in coil and fixes, carry out induction melting under high-purity argon gas protection, and molten metal liquid is blown into casting under certain pressure difference
Form amorphous alloy ribbon；It is 1.0MPa to blow pressure needed for casting, and vacuum degree is 9.0 × 10-4Pa blows casting amorphous alloy thin obtained
Bandwidth is 2mm, and thickness is 25 μm；
The sample that several 30mm long are intercepted on the amorphous alloy thin band of acquisition is placed in tube furnace, in the feelings of logical argon gas
Under condition, with 10 DEG C of min-1Speed from 25 DEG C of temperature programmings to 150 DEG C, after constant temperature keeps 2h, then with 5min-1Speed program
250 DEG C are warming up to, constant temperature takes out after keeping 3h.
Amorphous alloy ribbon obtained in the previous step is placed in 0.02M HF solution and takes off alloy treatment 6h, ligament and hole is made
The uniform nano porous copper of diameter.There is nano porous copper obtained uniform, co-continuous ligament/pore space structure three-dimensional (3D) to receive
Meter Duo Kong patterns.Unilateral nanoporous copper thickness is 10 μm, ligament width 30nm, aperture size 20nm.Then exist
0.2MH2SO4It is impregnated 70 seconds in solution.
Using platinum electrode as cathode, the nano porous copper prepared cleans, is used as anode to carry out electrochemical oxidation after drying,
Experiment condition is that will contain 0.6M NaOH and 0.3M Na2SO4Mixed solution as electrolyte, current density 15mA cm-2,
Reaction time 10min, 25 DEG C of reaction temperature；It is cleaned, is placed in drying box in 100 DEG C of dry 1h with deionized water after taking-up,
Obtain multi-stage porous nano porous copper load nano cuprous oxide wire composite material；7 μm of unilateral nano wire thickness, 7 μm of nanometer line length,
Wide 8nm, every 20~30 nano wire clusters are at a branch of.The porous of 0.5nm is had sizes of about on nano cuprous oxide wire.
The multi-stage porous nano porous copper load nano cuprous oxide wire composite material made from the present embodiment carries out photocatalysis
The experimentation of degradating organic dye is as follows：
Organic dyestuff rhodamine B and methylene blue is selected to carry out photocatalytic degradation experiment, solution is by 5ml 15mg L-1Sieve
Red bright B, 2ml 20mg L-1Methylene blue and 3ml 40wt.%H2O2Oxidant forms, using the xenon lamp of 500W as light
Source, xenon lamp between the solution that is degraded at a distance from be 10cm, intensity of illumination be 100mW cm-2.When experiment, multi-stage porous obtained is received
Rice Porous Cu load nano cuprous oxide wire composite material immerses in solution, investigates the test of solution after dyestuff degradation different time
Situation, the wherein relative absorbency of dyestuff are surveyed by ultraviolet-visible spectrophotometer (Lambda-750PerkinElmer)
Examination.Using composite material obtained in the present embodiment respectively to organic dyestuff rhodamine B degradation 0,1,2,3, after five minutes, by molten
The relative absorbency of liquid compares it is found that extending to 5 minutes at any time, dyestuff is degradable.The material carries out cycle degradation experiment,
It was found that being still more than 98% to the degradation rate for (each recycling 5min) after 5 cycles of congruent, different batches dyestuff degradation.It says
The bright made composite material of the present embodiment has the performance of good photocatalytically degradating organic dye.
Embodiment 3
Select alloying component Cu50Zr20Ti25Al5, the atomic percent according to each element in subject alloy：Cu is
50at.%, Zr 20at.%, Ti 25at.%, Al 5at.% weigh the high-purity copper sheet that mass fraction is 99.99%
(7.525g), zirconium grain (4.321g), titanium grain (2.835g) and aluminium flake (0.32g) obtain master alloy raw material 15g；By master alloy raw material
It is placed in vacuum arc melting furnace and (is put into the pure titanium grain of 99.9wt% before melting as oxygen scavenging material), under high-purity argon gas protection
Melt back 4 times (ensure the uniformity of alloy), each 40s or so.Cool to the furnace room temperature to get to
Cu50Zr20Ti25Al5Alloy pig.
3~4g of alloy pig after taking polishing to clean is placed in quartz test tube, and quartz test tube is put into vacuum and is got rid of in band machine and is felt
It answers in coil and fixes, carry out induction melting under high-purity argon gas protection, and molten metal liquid is blown into casting under certain pressure difference
Form amorphous alloy ribbon；It is 1.0MPa to blow pressure needed for casting, and vacuum degree is 9.0 × 10-4Pa blows casting amorphous alloy thin obtained
Bandwidth is 2mm, and thickness is 25 μm；
The sample that several 30mm long are intercepted on the amorphous alloy thin band of acquisition is placed in tube furnace, in the feelings of logical argon gas
Under condition, with 10 DEG C of min-1Speed from 25 DEG C of temperature programmings to 150 DEG C, after constant temperature keeps 1h, then with 10min-1Speed program
250 DEG C are warming up to, constant temperature takes out after keeping 1h.
Amorphous alloy ribbon obtained in the previous step is placed in 0.01M HF solution and takes off alloy treatment 8h, ligament and hole is made
The uniform nano porous copper of diameter.There is nano porous copper obtained uniform, co-continuous ligament/pore space structure three-dimensional (3D) to receive
Meter Duo Kong patterns.Unilateral nanoporous copper thickness is 12 μm, ligament width 40nm, aperture size 30nm.Then exist
0.25MH2SO4It is impregnated 60 seconds in solution.
Using platinum electrode as cathode, the nano porous copper prepared cleans, is used as anode to carry out electrochemical oxidation after drying,
Experiment condition is that will contain 1M NaOH and 0.5M Na2SO4Mixed solution as electrolyte, current density 20mA cm-2, instead
15min between seasonable, 20 DEG C of reaction temperature；It is cleaned with deionized water after taking-up, is placed in drying box in 150 DEG C of dry 1h, obtains
Nano cuprous oxide wire composite material is loaded to multi-stage porous nano porous copper；10 μm of unilateral nano wire thickness, 10 μm of nanometer line length,
Wide 5nm, every 20~30 nano wire clusters are at a branch of.The porous of 1.5nm is had sizes of about on nano cuprous oxide wire.
The multi-stage porous nano porous copper load nano cuprous oxide wire composite material made from the present embodiment carries out photocatalysis
The experimentation of degradating organic dye is as follows：
Organic dyestuff rhodamine B and methyl orange is selected to carry out photocatalytic degradation experiment, solution is by 8ml 15mg L-1Luo Dan
Bright B, 1ml 20mg L-1Methyl orange and 1ml 40wt.%H2O2Oxidant forms, using the xenon lamp of 500W as light source, xenon
Lamp between the solution that is degraded at a distance from be 10cm, intensity of illumination be 100mW cm-2.It is when experiment, multi-stage porous nanometer obtained is more
Hole copper load nano cuprous oxide wire composite material immerses in solution, investigates the test feelings of solution after dyestuff degradation different time
Condition, the wherein relative absorbency of dyestuff are surveyed by ultraviolet-visible spectrophotometer (Lambda-750PerkinElmer)
Examination.Using composite material obtained in the present embodiment respectively to organic dyestuff rhodamine B degradation 0,1,2,3, after five minutes, by molten
The relative absorbency of liquid compares it is found that extending to 5 minutes at any time, dyestuff is degradable.The material carries out cycle degradation experiment,
It was found that being still more than 97.8% to the degradation rate for (each recycling 5min) after 5 cycles of congruent, different batches dyestuff degradation.
Illustrate that the made composite material of the present embodiment has the performance of good photocatalytically degradating organic dye.
Comparative example 1：
The amorphous alloy ribbon of gained is directly carried out to de- alloy without Overheating Treatment, other conditions are the same as embodiment 1, gained
Nano porous copper it is frangible, mechanical integrity is destroyed.
Comparative example 2：
In heat treatment, with 20 DEG C of min-1Speed from 25 DEG C of temperature programmings to 150 DEG C, after constant temperature keeps 5h, then with
20min-1Speed program be warming up to 250 DEG C, constant temperature takes out band after keeping 0.5h.Other conditions take off alloy with embodiment 1
Still there is crackle appearance on the nano porous copper surface obtained afterwards.
Comparative example 3：
In anodized, select electrolyte for 0.05M NaOH, current density 40mA cm-2, the reaction time
90min, 10 DEG C of reaction temperature, other conditions do not have hole with embodiment 1, gained nano cuprous oxide wire surface.
The above comparative example is to implement the case of failure, and arbitrarily change preparation parameter of the present invention can lead to not obtain tough
The good nano porous copper of band/hole pattern or the cuprous nano wire of porous oxidation etc..
Heat treatment is had to pass through before the amorphous alloy ribbon obtained is carried out de- alloy；Heat is carried out to amorphous alloy ribbon
When processing, Temperature Programmed Processes cannot be changed arbitrarily, and the effect of removal internal residual stress is otherwise not achieved.At anodic oxidation
When reason, anodic oxidation experiment parameter need to be reasonably selected, otherwise the nano cuprous oxide wire effect of nano porous copper Surface Creation is not
Ideal, and then photocatalytically degradating organic dye performance is had an impact.
Unaccomplished matter of the present invention is known technology.
Claims (5)
1. a kind of multi-stage porous nano porous copper loads nano cuprous oxide wire composite material, which is strip, including non-
Brilliant matrix, the nano porous copper being covered on noncrystal substrate and the cuprous nanometer of porous oxidation for being supported on nano porous copper surface
Line；
Wherein, which is 5 layers, and intermediate core layer is noncrystal substrate, and intermediate core layer both side surface is covered with nanometer
Porous Cu, and the cuprous nano wire of porous oxidation in both sides nano porous copper area load；The noncrystal substrate is
CuxZryTizAlwAlloying component, wherein x, y, z, w are atomic percent, 45≤x≤50,20≤y≤25,25≤
Z≤30,5≤w≤10 and+w=100 x+y+z；Wherein unilateral 6 ~ 12 μm of nano porous copper thickness, tough bandwidth
20 ~ 40 nm, 15 ~ 30 nm of aperture size, 3 ~ 12 μm of unilateral nano wire thickness, 5 ~ 10 μm of nanometer line length, wide 5 ~ 10 nm, often
20 ~ 30 nano wire clusters are at a branch of；The nano aperture that size is 0.5 ~ 2 nm is dispersed on nano wire.
2. the preparation method of multi-stage porous nano porous copper load nano cuprous oxide wire composite material as described in claim 1,
It is characterized in that including the following steps：
The first step prepares amorphous alloy ribbon
According to target the proportioning of ingredient weighs pure Cu, pure Zr, pure Ti and pure Al；Melting system in vacuum arc melting furnace is put into after cleaning
Cu-Zr-Ti-Al alloy pigs are obtained, are placed in quartz test tube through polishing, cleaning, quartz test tube is put into vacuum and got rid of in band machine and is felt
It answers in coil and fixes, carry out induction melting under high-purity argon gas protection, molten metal liquid is blown into cast into AMORPHOUS ALLOY RIBBONS；
Wherein：Melting and get rid of band vacuum degree be 9 × 10-4Pa；It is 0.5 ~ 2.0 MPa to blow casting pressure；Blow casting non-crystaline amorphous metal item obtained
Bandwidth is 1.5 ~ 2 mm, and thickness is 20 ~ 40 μm；
Amorphous alloy ribbon is heat-treated by second step
Amorphous alloy ribbon obtained in the previous step is placed in tube furnace, in the case of logical argon gas, with 5 ~ 10 DEG C of min-1Speed
Degree is from 25 DEG C of temperature programmings to 150 DEG C, after constant temperature keeps 1 ~ 3 h, then with 5 ~ 10 DEG C of min-1Speed program be warming up to 250 DEG C,
Constant temperature takes out after keeping 1 ~ 3 h；
Third walks, and de- alloy treatment prepares nanoporous copper metal
Amorphous alloy strips obtained in the previous step are placed in 4 ~ 8 h of immersion in HF corrosive liquids, obtain nanoporous copper metal；Corrosion
Temperature is 298 K constant temperature, a concentration of 0.01 ~ 0.05 M of HF corrosive liquids；Then in the H of 0.1 ~ 0.25 M2SO460 are impregnated in solution
~ 90 seconds；
4th step, anodic oxidation prepare multi-stage porous nano porous copper load nano cuprous oxide wire composite material
Using platinum electrode as cathode, previous step passes through H2SO4The nanoporous copper metal that solution impregnates as DC power supply anode,
Carry out anodic oxidation；Composite material obtained is placed in drying box in 50 ~ 150 DEG C of dry 1 ~ 2 h, it is more to obtain multi-stage porous nanometer
Hole copper loads ultrafine cuprous oxide nanowire composite；
Wherein, in anodic oxidation reactions, the mixed solution of electrolyte sodium hydroxide and sodium sulphate, in mixed solution, NaOH's is dense
Degree is 0.5 ~ 1 M, NaOH and Na2SO4Molar ratio be 2:1；0.5 ~ 20 mA cm of current density-2, 5 ~ 60 min of reaction time,
20 ~ 30 DEG C of reaction temperature.
3. the preparation method of multi-stage porous nano porous copper load nano cuprous oxide wire composite material as claimed in claim 2,
The pure Cu, pure Zr, pure Ti and pure Al purity be mass fraction be 99.99%.
4. the application of multi-stage porous nano porous copper load nano cuprous oxide wire composite material as described in claim 1, special
Sign is for photocatalytically degradating organic dye.
5. the application of multi-stage porous nano porous copper load nano cuprous oxide wire composite material as claimed in claim 4, special
Sign is that the organic dyestuff is rhodamine B, one or more in methyl orange and methylene blue.
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